本研究係應用電化學氧化法處理異丁烷/烯烴之烷化製程衍生廢酸，藉由丁烯通入高濃度硫酸中，以模擬烷化製程所產生的廢酸，其有機物濃度約為10970~23770mg/L。本文中將探討影響有機物去除之操作變數效應，包括施予電壓、反應溫度、硫酸濃度及氧氣流量。實驗測試結果顯示電解電壓為5volt、反應溫度為298 K、硫酸濃度為96 wt%及通氧量120ml/min 的操作條件下，歷經12 小時之電解反應，有機物去除效率可達58%，而有機物之氧化降解主要是利用陰極還原氧氣所生成之過氧化氫，氧氣之主要來源殆為陽極上水份之電解。另一方面本研究嘗試利用電芬頓氧化法處理異丁烷/烯烴之烷化製程廢酸，惟處理效果並不理想，有機物去除率僅為，其原因殆為部份亞鐵離子於陰極上還原為金屬鐵，因而遮蔽部份鉑極板，使得氧氣還原為過氧化氫之產率降低。

In this study the electrochemical oxidation method is employed todispose the spent acid from isobutene/olefin alkylation process. The spentacid produced in the laboratory is by means of passing a butene streamthrough concentrated sulfuric acid, of which organic compoundsconcentration is 10970-23770 mg/L. Effects of operating parameters onthe performance of removal of organic compounds in spent acid havebeen investigated, including electrode potential, reaction temperature,sulfuric acid concentration and oxygen dosage. The removal percentageof TOC reaches 58% under the conditions of electrode potential = 5V, T =298 K, O2 = 120 ml/min and H2SO4 = 96 wt% after the duration of 12 hrs.The phenomenon observed is attributed to the oxidizing agentelectrogenerated in the cathode, wherein the oxygen is reduced intohydrogen peroxide. The oxygen gas is believed to mainly derive fromwater electrolysis in the anode. In another respect, the degradation oforganic compounds in spent acid using Electro-Fenton method has alsobeen conducted. The removal percentage of organic compounds is merely%. The observation may be explained by the reduction of ferrous iron inthe cathode, which would block some active sites for electrogeneration ofhydrogen peroxide.

目 錄中文摘要 ----------------------------------------------------------------------------- i英文摘要 ----------------------------------------------------------------------------- iii致謝 ----------------------------------------------------------------------------- v目錄 ----------------------------------------------------------------------------- vi圖目錄 ----------------------------------------------------------------------------- ix表目錄 ----------------------------------------------------------------------------- xi一、 前言1-1 研究緣起--------------------------------------------------------------- 11-2 研究目的與內容---------------------------------------------------- 2二、 背景資料與文獻2-1 烷化石油--------------------------------------------------------------- 42-2 烷化反應介紹-------------------------------------------------------- 42-2-1 熱烷化法--------------------------------------------------------------- 42-2-1 觸媒烷化法----------------------------------------------------------- 52-3 廢硫酸再生技術---------------------------------------------------- 72-4 電解氧化原理-------------------------------------------------------- 82-4-1 直接氧化--------------------------------------------------------------- 192-4-2 間接氧化--------------------------------------------------------------- 20vii2-5 高級氧化程序-------------------------------------------------------- 21三、 研究方法3-1 實驗材料--------------------------------------------------------------- 253-2 實驗藥品--------------------------------------------------------------- 273-3 實驗分析儀器-------------------------------------------------------- 303-4 實驗裝置--------------------------------------------------------------- 323-5 電解反應系統-------------------------------------------------------- 333-6 實驗流程--------------------------------------------------------------- 343-7 實驗分析原理-------------------------------------------------------- 353-7-1 總有機碳含量(TOC)----------------------------------------------- 353-7-2 過氧化氫濃度測定------------------------------------------------- 353-7-3 Fe3+鐵離子濃度測定----------------------------------------------- 363-7-4 氣相層析質譜儀(GC/MS)---------------------------------------- 373-7-5 Karl- Fischer 水份檢測----------------------------------------- 39四、 結果與討論----------------------------------------------------------- 414-1 實驗前處理----------------------------------------------------------- 414-2 間接電解氧化法---------------------------------------------------- 414-3 廢酸電解中間物之鑑定------------------------------------------ 514-4 電芬頓氧化法-------------------------------------------------------- 56viii五、 結論---------------------------------------------------------------------- 59參考文獻 ----------------------------------------------------------------------------- 61

1. Albright LF. and Goldsby AR. ,”Industrial and LaboratoryAlkylation”American Chemical Society Symposium Series55 p. 284，1977.2. Ken Kranz Managing R&D Chemist,”ALKYLATIONCHEMISTRY”,STRATCO, 2003.3. Fenton H. J. H., Oxidation of Tartaric Acid in Presence of Iron,J.Chem. Soc. Vol.65 , p.899 , 1894.4. Gernjak W., Malato S., Krutzler T., Glaser A., Caceres J., Bauer R.,Fernandez-Alba A. R. , Photo-Fenton treatment of water containingNatural phenolic pollutants, Chemosphere, 50, 71 , 2003.5. Birame Boye a, Momar Morie`me Dieng b, Enric Brillas a,*Anodicoxidation, electro-Fenton and photoelectro-Fenton treatments of2,4,5-trichlorophenoxyacetic acid ,Journal of ElectroanalyticalChemistry 557 p.135，2003.6. Ventura A.，Jacquet G.，Bermond A.，Camel V.，Electrochemicalgeneration of the Fenton’s reagent application to atrazine degradation，Water research 36，p.517，2002.7. Boye B.，Brillas E.，Dieng M. M.，Electrochemical degradation of theherbicide 4-chloro-2methylphenoxyacetic acid in aqueous medium byperoxi-coagulation and photoperoxi-coagulation，Journal ofElectroanalytical Chemical 540，p.25，2003.8. Gnann M.，Gregor C. H.，Schelle S.，Chemical oxidative process forpurifying highly contained wastewater，WO patent 93/08129，Peroxid-Chemie GmbH，DE，1993.9. Brillas E.，Calpe J. C.，Casado J.，Mineralization of 2,4-D by advancedelectrochemical oxidation processes，Wat. Res. Vol.34，No.8，p. 2253，2000.10. Parvinen L. and Salli J.,W.O.9,713,567.11. Plessen H.V.and Schiessler S., U.S. Patent 3,972,987, 1976.12. Stefan H.Bossmann,Esther Oliveros,Sabine Göb,SilviaSiegwart,Elizabeth P.Dahlen,Leon Payawan,Jr.,MatthiasStraub,Michael Wörner,and André M.braun，New Evidence againstHydroxyl Radicals as Reactive Intermediates in the Thermal andPhotochemically Enhanced Fenton Reaction，J.Phys.Chem.A,102,5542-5550, 1998.13. Chou T. C. and Chen Y. L., “Recovery and Regeneration of SulfuricAcid”,U.S. Patent 5, 547, 655., 1996.14. Mazzfro W. J., Clarke S. I., Taylor P. N., “Process for Purification andConcentration of Sulfuric Acid.” , U.S. Paten 5, 275, 701., 1994 .15. 柯清水著，石油化學概論，正文書局p.119，1992.16. 陳文星，洪正宗，蔡坤榮”烷化廢硫酸之電解回收”，石油季刊第34 卷第三期，p.1，1998。17. 梁景松，電化學氧化法應用於TNT 製程廢酸中有機物去除之研究，國立雲林科技大學化學工程系碩士班，碩士論文，2007。18. 郭桓志，異丁烷/烷烴烷化製程廢酸中有機物去除之研究，國立雲林科技大學化學工程系碩士班，碩士論文，2007。19. 林昇志，電化學氧化法應用於三硝基甲苯製程中有機物去除之研究，國立雲林科技大學化學工程系碩士班，碩士論文，2008。20. 張博荀，H2O2/Fe2+化學氧化法處理反應性染料-Black B 之研究，國立成功大學化學工程研究所，碩士論文，2004。21. Gurol,M.D.,Bremen,W.M.,And Holden,T.E.”Oxidation of Cyanides inIndustrial Wastewaters by Ozone.”Environ. Progr.4,1:46-51,1985.22. 賴耿陽，廢棄物處理工學，復文書局，1993。23. 陳文星，蘇維彬，洪正宗，”烷化廢硫酸之再生”，石油季刊第34 卷第一期，p.37，1998。24. Pignatello J.,“Dark and photoassisted Fe3+- catalyzed degradation ofchlorophenoxy herbicides by hydrogen peroxide.”, Environ. Sci.Technol. 26 , p. 944,1992.25. Zuo Y., Hoign_e J., "Formation of hydrogen peroxide and depletionof oxalic acid in atmospheric water by photolysis of iron(III)–oxalatocomplexes.”, Environ. Sci. Technol. 26,p. 1014., 1992.26. 阮建能，TNT 製程廢酸中有機物去除之研究，國立雲林科技大學化學工程系碩士班，碩士論文，2004。27. Do J. S., Chen C. P.,“In situ oxidative degradation of formaldehydewith hydrogen peroxide electrogenerated on the modified graphites”,J.Appl. Electrochem., 24, p. 936 , 1994.28. 田福助「電化學-理論與應用」，高立圖書出版社，1985。29. Yuan S., Tian M., Chi M. Y., Lin L., Lu X., “Treatment ofnitrophenols by cathode reaction and electro-Fenton methods.”,Journal of Hazardous Materials B137, p. 573 ,2006.30. Lunar L., Sicilia D., Rubio S., Perez-Bendito D. and Nickel U.,“Degradation of photographic developers by Fenton reagent:conditionoptimization and kinetics for metal oxidation”, Wat. Res. 34p. 1791 , 2000.